Color developers containing an aromatic primary amine color-developing agent have been widely used conventionally for a long time for the formation of color images, and at present they play a major role in the method for forming images of color photographs. However, the above color developers have the problem that they are very readily oxidized by air or a metal, and it is well known that when a color image is formed by using an oxidized developer, desired photographic performance cannot be obtained because fogging increases or the sensitivity or gradation changes.
In particular, as the time of the processing step is shortened, as is common today, the change of photographic performance at the time of continuous processing is apt to become large, and in some cases, a serious problem leading to color stains arises. In particular, when the desilvering step or the washing step is shortened, or when the processing amount per unit of time is small, the above problem is apt to arise.
As causes leading to color stains under these circumstances, there are many considerations. For instance:
A: The color developer deteriorates with time, the photographic performance changes, the oxidized product of the developing agent adheres to the photographic material, and therefore the rinsing becomes insufficient, bringing about color stains. PA0 B: The color-developing agent is carried in the bleaching solution or the bleach-fix solution and is oxidized therein, causing fogging or stains. PA0 C: Dissolved-out materials from the photographic material accumulate in the color developer and adhere to the photographic material, causing color stains. PA0 D: The washing out of the dyes and sensitizing dyes contained in the photographic material is not sufficient, thereby the photographic material remains colored. PA0 E: The bleach-fix solution or the washing water or the stabilizing solution placed after the bleach-fix solution deteriorates with time, causing color stains.
In order to solve problem A in particular, it is necessary to improve the stability of the color developer, and many studies have been made.
For instance, in order to improve the stability of color developers, various preservatives and chelating agents have been studied. For example, as preservatives can be mentioned aromatic polyhydroxy compounds described, for example, in JP-A ("JP-A" means unexamined published Japanese patent application) Nos. 49828/1987, 160142/1984, and 47038/1981 and U.S. Pat. No. 3,746,544, hydroxycarbonyl compounds described in U.S. Pat. No. 3,615,503 and British Patent No. 1,306,176, .alpha.-aminocarbonyl compounds described in JP-A Nos. 143020/1977 and 89425/1978, alkanolamines described in JP-A No. 3532/1989, and metal salts described in JP-A Nos. 44148/1982 and 53749/1982. As chelating agents can be mentioned aminopolycarboxylic acids described in JP-B ("JP-B" means unexamined Japanese patent publication) Nos. 030496/1973 and 30232/1969, organic phosphonic acids described in JP-A No. 97347/1981 and JP-B 39359/1981 and West German Patent No. 2227639, phosphonocarboxylic acids described, for example, in JP-A Nos. 102726/1977, 42730/1978, 121127/1979, 126241/1980, and 65956/1980, compounds described, for example, in JP-A Nos. 195845/1983 and 203440/1983 and JP-B No. 40900/1978, and organophosphonic acid chelating agents described in Research Disclosure Nos. 18837 and 17048.
However, even if these preservation-improving techniques are employed, coloring and deterioration of color developers cannot be completely prevented. Further, although sulfite ions are effective in preventing developers from coloring, they cannot be used in a large amount for such as black-and-white developers, because sulfite ions harmfully affect the color formation or have a solvent effect on silver halides. Additionally, recently it is preferred that sulfite ions not be used in view of the improvement of color formation, and therefore coloring of color developers is becoming a further serious problem.
Although hydroxylamine compounds are described as preservatives (antioxidantas) for color developers, for example, in JP-A Nos. 106655/1988 and 5341/1988 and WO 87/04534, for rapid processing or for a small amount of processing, as in the present invention, they are not adequate to prevent color stains from occurring.
To prevent color stains due to deterioration of color developers over time as stated above, it is necessary to prevent the color developer from being oxidized, and also it is required that adhesion, mainly of the oxidized product (contaminant) of the developing agent in the color developer, is reduced and that the oxidized product of the developing agent is washed out in the subsequent step, to lessen color staining.